Compositions and process to increase the wet strength of paper



Unitcd States Patent 3,138,473 COMPOSITIONS AND PROCESS TO INCREASE THE WET STRENGTH OF PAPER Don E. Floyd, Robbinsdale, Richard J. Ess, Minneapolis, James L. Keen, New Brighton, and Joseph W. Opie, Minneapolis, Minn., assignors to General Mills, Inc., a corporation of Delaware No Drawing. Filed Jan. 26, 1962, Ser. No. 169,100 8 Claims. (Cl. 106205) This invention relates to compositions which are useful in the manufacture of high wet-strength felted fibrous cellulosic materials such as paper, board, shaped paper articles and the like. More particularly, this invention relates to wet-strength imparting compositions consisting essentially of certain fatty-derived amino-containing compounds admixed with modified polysaccharides. Moreover, this invention includes the process whereby these amino compound polysaccharide compositions are employed to obtain high wet-strength articles, and the improved felted fibrous cellulosic products therefrom.

Wet-strength, as it has come to be known in the manufacture of paper articles, is of importance in two major types of products. Wet-strength which does not sacrifice absorbency is required in the manufacture of disposable tissues and paper towels. Generally speaking, the natural gums and starches, particularly their dialdehyde or periodate oxidized forms, are used in imparting Wet-strength of this type. On the other hand, in the manufacture of such items as beverage cases, cardboard cartons, paper board, and the like, a wet-strength of quite a different type is required. Where the article must withstand continued or repeated contact with water, or must perform in highly humid atmospheres, a more or less permanent wet-strength is required. Absorbency is not required. Commercially, the formaldehyde-based resins, such as melamine-formaldehyde and urea-formaldehyde resins, are used to impart permanen wet strength to manufactured paper articles.

Compositions of the present invention are of the type which impart permanent wet-strength, such as is needed in paper board, carbons, wrapping paper, etc.

The compositions of the present invention offer important advantages as contrasted to commercially available resinous compositions yielding comparable results.

Two disadvantages have been attributed to the commercially available resinous compositions, such as melamineformaldehyde and urea-formaldehyde resins. The application of these type resins is limited generally to acid pHs, often aggravating equipment corrosion, and negating their use in alkaline or neutral pulps. Secondly, in order to obtain the desirable permanent wet-strength, the use of formaldehyde-based resins usually requires some sort of post-cure of the manufactured paper article to obtain optimum wet strength. This post-cure is usually accomplished by employing elevated drying temperatures, or heating the finished article, or storage for relatively long periods to allow the cure to proceed at room temperature. Additional steps such as these result in additional expense either in the form of steam requirements, time, labor and/ or warehousing.

The compositions of our invention on the other hand, will impart wet-strength when employed over a broad range of pH, from well on the acid side to well into the alkaline range. This affords versatility as to their use in acid pulps, alkaline pulps, or neutral pulps. It also allows the mitigation of corrosion by eliminating the need for an acid environment to obtain optimum results. Secondly, the compositions of our invention will impart Wetstrength without the necessity of post-cure of the paper product. Permanent wet-strength is observed immediately upon the application of the wet-strength additive of 3,138,473 Patented June 23, 1964 our invention to the paper product. This has the obvious advantage of a savings in time, materials, and labor.

An object therefore of the present invention is to provide useful compositions for the manufacture of high wetstrength felted fibrous cellulosic articles.

A further object is to provide compositions which will impart wet-strength when applied over a broad range of pH including alkaline pHs, and which will impart wetstrength without the necessity of increased temperature or a post-cure.

Still further objects are to provide improved processes whereby high wet-strength articles are obtained, and to provide the improved high wet-strength articles themselves. i

The fatty-derived amino-containing compounds of the present invention cover a broad variety of structures. They are the amino-amides and amino-imidazolines derived from the reactions of long chain carboxylic acids and alkylene polyamines, such as fat acid amino-amides, fat acid amino-imidazolines, amino-amides and aminoimidazolines from epoxidized fat acids, and the aminoamides and amino-imidazolines derived from polymeric fat acids. A useful characterization of this class of compounds is amine number, i.e., the milligrams of potassium hydroxide equivalent to the amine groups in one gram of product. The amine number of a particular compound indicates the amine groups available for reaction and serves as an indication of structure. In general, the amino compounds found suitable in accomplishing the objects of this invention are those with amine numbers from about 50 to about 700.

The term fat acids is intended to include the various saturated, ethylenically unsaturated and acetylenically unsaturated naturally occurring and synthetic monobasic aliphatic acids containing from 8-24 carbon atoms. Suitable saturated fat acids include branched and straight acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Another class of suitable acids includes the branched straight chain, poly and mono ethylenically unsaturated acids such as 3-octanoic acid, ll-dodecanoic acid, linderic acid, lauroleic acid, myristoleic acid, tsuzuic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, cetoleic acid, nervonic acid, linoleic acid, linolenic acid, eleostearic acid, hiragonic acid, moroctic acid, timnodonic acid, eicosatetraenoic acid, nisinic acid, scoliodonic acid and chaulmoogric acid. Also included are the acetylenically unsaturated fat acids. Suitable examples of such materials include 10- undecanoic acid, tariric acid, stearolic acid, behenolic acid, and isamic acid.

The term polymeric fat acid refers to polymerized fat acids. The term polymeric fat radical refers to the hydrocarbon radical of a polymerized fat acid, and is generic to the divalent, trivalent, and other polyvalent hydrocarbon radicals of dimerized fat acids, trimerized fat acids and higher polymers of fat acids. The divalent and trivalent hydrocarbon radicals are referred to herein as dimeric fat radical and trimeric fat radical respectively.

The saturated, ethylenically unsaturated, and acetylenically unsaturated fat acids are generally polymerized by somewhat different techniques, but because of the functional similarity of the polymerization products, they all are generally referred to as polymeric-fat acids.

Saturated fat acids are difficult to polymerize but polymerization can be obtained at elevated temperatures with a peroxidic catalyst such as di-t-butyl peroxide. Because of the generally low yields of polymeric products, these materials are not currently commercially significant. Suitable saturated fat acids include branched and straight chain acids, and are described above.

The ethylenically unsaturated acids are much more readily polymerized. Catalytic or non-catalytic polymerization techniques can be employed. The non-catalytic polym erization generally requires a higher temperature. Suitable catalysts for the polymerization include acid or alkaline clays, di-t-butyl peroxide, boron trifiuoride and other Lewis acids, anthroquinone, sulfur dioxide and the like. Suitable monomers include the branched straight chain, poly and mono ethylenically unsaturated acids described above.

The acetylenically unsaturated fat acids can be polymerized by simply heating the acids. Polymerization of these highly reactive materials will occur in the absence of a catalyst. The acetylenically unsaturated acids occur only rarely in nature and are expensive to synthesize. Therefore, they are not currently of commercial significance. Any acetylenically unsaturated fat acids, both straight chain and branched chain, both mono-unsaturated and poly-unsaturated, are useful monomers for the preparation of the polymeric fat acids. Suitable examples of such materials are described above.

Because of their ready availability and relative ease of polymerization, oleic and linoleic acid are the preferred starting materials for the preparation of the polymeric fat acids. Polymerizations using alkaline or acid clay catalysts or heat are the preferred methods of preparation.

The epoxy fatty acid compounds, i.e., epoxidized fatty acid esters and acids, also employed as raw materials of the present invention may be prepared in any one of the known methods. One method is to react any of the various unsaturated fatty acids mentioned previously with peracetic acid at about room temperature. The peracetic acid may be performed before the epoxidation step or formed in situ by any one of the well-known processes invoving sulfonic acid resins utilizing hydrogen peroxide and acetic acid. Epoxidation can also be performed by the use of formic acid and hydrogen peroxide. The epoxides can also be prepared by addition of hypochlorous acid to the carbon-carbon double bond followed by dehydrochlorination, i.e.

The polyamines which may be employed in preparing the amino-containing compounds of our invention are the alkylene polyamines such as ethylene diamine, diethylene triamine, tetraethylene pentamine, di-1,3-propane triamine, di-1,2-propane triamine, and the like. The polyamines can be represented by the formula H N(RNH) H where R is an alkylene radical and n is an integer from 2 to 6. While the alkylene radical is generally ethylene, alkylene radicals having up to 6 carbon atoms are suitable. The ethylene-type compounds are generally more readily available and are the preferred starting materials for the aminocontaining compounds of this invention.

The amino-containing compounds of the present invention are derived by the reaction of an alkylene polyamine of the type discussed above with the acid or ester form of the above discussed fatty derived carboxylic acids, under conditions which result in unreacted amino groups.

The fat acid arnino-irnidazolines of the present invention are the products of the reaction of the previously mentioned alkylene polyamines and the above-mentioned saturated or unsaturated fat acids. Essentially one equivalent of fat acid is reacted with one mole of polyamine. The reaction is carried out under the usual conditions employed for this purpose, that is generally, a reaction at up to about 300 C. for up to several hours. During this reaction dehydration to the monoamide proceeds initially, followed by further dehydration to the imidazoline ring.

Thus, even with the simplest alkylene polyamine, ethylene diamine, a compound is formed which has a free amino group-in this case, a secondary amine group. However, generally speaking, it is preferred to use one of the higher alkylene polyamines, such as diethylene triamine, triethylenetetramine, tetraethylene pentamine, etc., so as to obtain compounds having a free primary amine group as well as one or more secondary amine groups. The amino-imidazolines prepared have amine numbers in the range of about 50 to about 500.

The fat acid amino-amides of the present invention are prepared in a manner similar to the amino-imidazolines above. Essentially one equivalent of fat acid is reacted with one mole of alkylene polyamine. However, the amidification reaction is carried out at a generally lower temperature, usually at about 170 C. for several hours. This results in fatty amino-amides containing free primary amino groups in all cases, and both free primary amino groups and one or more secondary amino groups, where the alkylene polyamine employed is of the type of diethylene triamine or higher.

The amino-polyamides and the amino-polyimidazolines of the present invention derived from the reaction of alkylene polyamines and polymeric fat acids are prepared by methods analogous to the mono-amides and mono-imidazolines described above, that is to form only, or essentially only, amide linkages, the reaction is usually carried out at 200 C. or less, for a period of several hours. On the other hand, when it is desired to obtain imidazoline linkages, the reaction is carried on at about 300 C. for several hours.

If the epoxidized fat acids or their esters are employed, complex amino-containing imino-linked polyamides-polyimidazolines result. The reaction with the polyamine may be controlled to obtain products containing mainly amide groups, or substantially all imidazoline groups, or mixtures. Conditions under which these products are prepared vary greatly, particularly as the starting material varies from essentially all epoxidized fat acid or essentially all ester, or mixtures. In general, where the starting material is predominantly ester, reaction with the polyamine proceeds quite readily, and amide groupings are formed at temperatures as low as C., and imidazoline formation is appreciable, even at C. However, when the starting material is predominantly free acid, the temperatures of dehydration are significantly higher, requiring as high as 200 to 300 C. to convert to essentially all imidazoline groups. The modified polysaccharides of the present invention are of essentially two types. These are: (1) periodate modified guar or locust bean gum in which substantially only the galactose units have been oxidized, and (2) periodate modified starches of varying degrees of oxidation up to and including products wherein substantially all of the units (anhydroglucose) are oxidized.

The periodate oxidation of a polysaccharide has been shown to proceed through the oxidation of an anhydrous hexose unit to a dialdehyde as per the following reaction:

CHzOH CHzOH p0 a. H O I 0 4 O as as H 0 H H H n O O n In the case of periodate oxidized starches, which are composed essentially of anhydroglucose units, the oxidation is more or less random throughout the chain and the degree of oxidation is dependent almost entirely upon the amount of oxidizing agent employed. On the other hand, the periodate oxidation of polygalactomannan gums proceeds somewhat differently. The anhydrogalactose units are preferentially attacked before the anhydromannose units. Hence, the oxidation of a polygalactomannan gum is not random, but is selective for the anhydrogalactose units at low levels of oxidation.

The partially oxidized polygalactomannan gums of the present invention are conveniently prepared by treatment with less than stoichiometric amounts of periodate (usually in the range of 0.01 to 0.4 mole per mole of anhydrous hexose unit) under which conditions the anhydrogalactose units are preferentially attacked before the anhydromannose units. This reaction may be carried out as a solution reaction in aqueous systems, as a suspension reaction in aqueous systems containing an organic solvent such as an alcohol or ketone, or under substantially dry conditions of blending the reactants. In this reaction, the degree of oxidation of the anhydrogalactose units is governed by the conditions and the mole ratio of periodate. The ratio of anhydrous galactose units to anhydrous mannose units varies with the particular polygalactomannan gum in question. The percentage of the galactose units which are oxidized can vary from a low value, of the order of 15 to 20%, on up to essentially all the galactose units oxidized. A typical product of this type is the aldehyde locust bean gum used as a standard material in the examples of the present invention. This product is shown to be oxidized. That is, l in 10 of the hexose units are converted. Since locust bean gum is comprised roughly of four mannose units to every one galactose unit and since galactose units are preferentially oxidized, this gum is one in which about 50% of the available galactose has been converted. It is these partially oxidized galactomannan gums that are the preferred polysaccharides in the compositions of the present invention.

When higher levels of periodate (in the range of 0.4 to 1.0 mole per mole of anhydrose hexose unit) are employed in the oxidation of polygalactomannan gums, both the anhydrogalactose units and the anhydromannose units are oxidized. This results in a product with a high degree of dialdehyde functionality, and quite similar in nature to the highly oxidized starches.

Oxidized starches, commercially available as dialde hyde starch, are derived from the oxidation of starches such as cornstarch, wheat starch, tapioca, etc. with periodate under conditions wherein the anhydroglucose units are converted to the dialdehyde functionality. The degree of oxidation attained in these reactions, is dependent to a great extent on time and amount of oxidizing agent employed. Reaction conditions can be essentially those as described for the preparation of oxidized polygalactomannan gums. The degree of oxidation can vary from a relatively low level, -20%, up to essentially completely oxidized, 90% or higher.

The fat acid derived amino-amide amino-irnidazoline/ oxidized polysaccharide compositions of our invention are applicable vto a wide variety of fibrous cellulosic materials, such as those commonly referred to as sulfite, soda, sulfate, and ground wood stock, or fibers derived from rag, cotton, bast, flax and stem fibers such as straw, or from repulped broke.

The compositions of our invention can be applied to the felted cellulosic products by tub application methods wherein the partially dried article is immersed in an aqueous solution or dispersion of the modified poly-- saccharide/amino-compound mixture and impregnated with about 110% thereof, based on the dry weight of the paper. The paper is then processed in the conventional manner. It is possible also to spray the formed paper product with an aqueous and/or alcohol solution or dispersion of the mixture.

The preferred process of the present invention, however, is the addition of an alcohol and/ or water solution or dispersion of the composition to the pulped and preferably refined cellulosic fiber. The composition is added in the beater, stock chest, head box or at any suitable agitated for 2 hours.

point ahead of the actual paper-forming operation. .Conditions are adjusted so as to obtain a concentration of about 0.1 to 10% based on the dry Weight of the fibers. The concentration of the polysaccharide/amino-compound mixture in the beater, for example, would be in the range of about 0.011% based on the pulp mixture.

The compositions of the present invention may be used alone or in conjunction with other additives commonly used in the manufacture of paper articles. The combination may be added as a solution or a dispersion in water, in water/alcohol, or other suitable solvent. The individual components may be added separately to the pulp mixture.

The following will serve to illustrate further our invention. The examples are illustrative and not to be .construed as limiting. Parts and percentages are by weight unless specifically stated otherwise.

Example I Wet end wet-strength additives can be elevated by well-known laboratory procedures consisting of the formation of hand sheets fabricated to contain the desired level of additive (or no additive) under carefully worked out, standardized, and rigidly adhered to procedures, followed by equilibration of the hand sheets under the desired conditions and determining the wet burst (and usually the dry burst) strengths of the sheets. Comparison is with a control, said control often consisting of a well-known standard wet-strength additive.

The following standard procedure was employed to evaluate the additives of the present invention:

360 grams (moisture free basis) of bleached kraft fibers was added to 24 liters of tap water and vigorously The pulp mixture was beaten in a Valley Laboratory Beater for 35 minutes, and then diluted with 24 liters of tap water. The pulp mixture was now ready to use to form hand sheets with various beater additives.

The additives were added to the pulp mixture as 1% aqueous solutions or emulsions, except for several additives which would not form aqueous solutions or emulsions, and these exceptions were added as 5% solutions in isopropanol. In every case 0.4 gram of additive was added to 2 liters of pulp mixture, and this amount of additive is equal to about 2.5% of the dry pulp weight. One sheet was formed from each liter of pulp mixture, so each result given in this application is the average wet-strength burst value of two sheets. In a number of tests the pH of the pulp mixture was changed by'the addition of concentrated HCl or 30% NaOH solution before the addition of the chemicals being tested. The additives were mixed with the pulp mixture for 10 minutes before hand sheets were prepared.

The hand sheets wereforrned with a Noble and Wood Sheet Machine, conditioned overnight at 73 F. and 50% R.H., immersed in tap water exactly 15 minutes, and wet burst values measured with a'Mullen Tester. The property measured on the hand sheets Was the Wet burst value, and this value'is expressed in units of pounds per pounds of ream weight, 25 x 40 x 500.

Sheets were run in replicate. obtained for each sheet.

A comparison standard of 0.4 gram of dialdehyde locust bean gun added to the pulp mixture (which had Ten burst values were previously been adjusted to a pH of about 3.6) was made Using the standard procedure outlined above, aldehyde locust beam gum was compared with mixtures comprising 3 parts aldehyde locust bean gum and 1 part aminocontaining compound. The wet-strength additives were added to the pulp at a level of 0.4 gram per 2000 ml. pulp mixture, or about 2.5% additive based on dry weight of pulp. Data were as follows:

1 See description supra. 1 Pounds per 100 pounds of ream weight, average data on duplicate sheets (average of for each sheet).

Example 11 The wet and dry burst resulting from combinations of the polymeric fat acid amino-imidazoline of Example I4 (amine No.=350400) and aldehyde locust beau gum were determined as a function of pH, concentration of additive, and ratio of the two components. The method was that described above. Bleached kraft pulp was 8 Example IV The retention of wet-strength after soaking (comparable to a beverage carton in wet service) was determined for the 30:70 amino-imidazoline:aldehyde locust bean gum combination of Example III. A series of hand sheets were prepared using the method described earlier, with the pH in the sheet mold measured at pH 7.08.0. The wet burst of these sheets was then determined by the method described earlier, except that the equilibration of the paper in water was carried out at various pHs and for times up to 9 days. An equilibration of minutes is the normal procedure for a wet-strength test without regard for permanency. Data were as follows:

A fat acid amino-imidazoline was prepared by reactused. Beating time was 35 minutes. Data were as mg 65 g. of tall 011 fatty acids (iodine value: 13 5 with follows: 4.0 equivalents g. of triethylene tetramme. Said re- Additive Composition Dry Burst, Percent Additive 2 Wet Burst, Percent Additive 2 Polymeric tat acid Aldehyde pH in amino'imidlocust Sheet azoline of bean gum, Mold Example percent I4, Percent 0 0.5 1.0 2.5 5.0 0 0.5 1.0 2.5 5.0

1 Each value is the average of average burst values from 3 hand. sheets expressed in lbs/100 lbs. ream weight.

1 Additive based on dry pulp Weight. a (1) =very slight \vet burst.

Example Ill Based on the data in Example III, a 30:70 ratio of the polymeric fat acid amino-imidazoline of Example I4 and aldehyde locust bean gum was selected as near optimum (particularly at pH 8.0-8.5). This ratio was then tested over a wide range of pH. Data were as follows:

action was carried out at 300 C. for 3 hours, removing the water of dehydration. The product had an amine number of 345 and a viscosity of 4 poises at 25 C.

The above fat acid amino-imidazoline (30 parts) was added along with aldehyde locust bean gum (70 parts) to bleached kraft fibers as per the method of Example I.

Dry Burst, Percent Additive 1 Wet Burst, Percent Additive a pH in Sheet Mold 2. 5-3. 0 159 165 180 187 0 19 34 63 87 4. 0-5. 0 149 156 164 177 183 0 18 34 58 79 6. 5-7. 0 154 163 173 188 192 0 12 26 55 79 8.0-8.5 159 182 0 9 24 57 78 9.5 162 154 160 163 177 0 3 (1) 9 18 38 10.2 147 151 147 133 131 0 5 (1) a (l) a (1) 6 1 Each value lbs. ream weig 2 Additive based on dry pulp weight. a (1) =very slight wet burst.

Hand sheets were prepared, and the wet burst determined as in Example I. The pH of the pulp dispersion was 4.5-5.0. Wet burst was 57 pounds per 100 pounds of ream weight. The wet-strength was of a permanent type.

Example VI A mixture of tall oil fatty acids and methyl esters of tall oil fatty acidshaving an oxirane number of 2.0 (epoxidation with peracetic acid), 50.5 g., was reacted with tetraethylene peutamine, 49.5 g., at 165 C. for two hours. The reaction product was then vacuum stripped to remove water and other volatiles. The resulting product (mainly an imino-linked aminoamide) had an amine number of 602.

The above aminoamide (25 parts) was added along with aldehyde locust bean gum (75 parts) to bleached kraft fibers as per the method of Example I. Hand sheets were prepared, and the wet burst determined as in Example I. The pH of the pulp dispersion was 3.6. Wet burst was 54 pounds per 100 pounds of ream weight. The wet-strength was of a permanent type.

Example VII Dialdehyde starch (90% oxidized) was combined with the polymeric fat amino-imidazoline of Example I-4. Wet-strength was determined on hand sheets prepared from pulp treated at three pHs at a level of 0.4 g. additive (3 parts dialdehyde starch, 2 parts amino-imidazoline) per 2000 ml. pulp mixture (2.5% additive based on dry Weight of fiber). Results were as follows:

Run VII-1:

Dialdehyde starch, g 0.24 Polymeric fat acid arnino-imidazoline, g 0.16 Wet burst:

pH 9.8 pH 8.6 20 pH 4.9 10

1 From Example I-4. 2 Lbs. 100 lbs. ream weight.

Example VIII Guar gum was oxidized with periodate to a level of 10% oxidation, that is one in ten of the hexose units were oxidized. Since guar gum contains on the average two anhydromannose units for every one anhydrogalactose unit, this results in about three galactose units oxidized to the dialdehyde functionality out of every ten galactose units present. This product was tested for wetstrength using the method of Example I. Bleached kraft was used, beating was for 35 minutes, pH was adjusted to pH 7.5-8.0. Results were as follows:

1 Lbs/100 lbs. ream weight. 2 Based on dry weight of pulp fibers.

From the above examples, it is evident that a wide variety of fat acid derived aminoarnide or amino-imidazoline compounds are effective in imparting wet-strength to paper when employed in combination with polysaccharides, either of the galactomannan gum type or conventional starches, of varying degrees of oxidation. It is evident that this wet-strength is of the permanent type, that is of the type required for paper board, beverage cartons, box board, and the like. This permanen wetstrength has been obtained by the simple addition of the additive to the paper pulp. No curing, either at elevated temperatures or for prolonged periods, is required.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In a process for the manufacture of felted fibrous cellulosic articles the step which comprises adding to the cellulosic fibrous material from about 0.1% to about 10% based on dry weight of cellulosic fiber, of a-mixture comprising (A) from about 15 to about percent by weight of a modified polysaccharide selected from the group consisting of oxidized polygalactomannan gums, and oxidized starches, and (B) from about 85 to about 15 percent by weight of a fat acid derived amino-containing compound having an amine number from about 50 to about 700 selected from the group consisting of the aminoamides and amino-imidazolines of fat acids, the aminoamides and amino-imidazolines of epoxidized fat acids, and the aminoamides and amino-imidazolines of polymeric fat acids.

2. In a process for the manufacture of felted fibrous cellulosic articles the step which comprises adding to the cellulosic fibrous material from about 0.1% to about 10% based on dry weight of cellulosic fiber, of a mixture comprising (A) from about 15 to about 85 percent by weight of a polygalactomannan gum modified by treatment with from 0.01 to 0.4 moles periodate per mole of anhydrous hexose unit and (B) from about 85 to about 15 percent by weight of a fat acid derived amino-containing compound having an amine number from about 50 to about 700 selected from the group consisting of the aminoamides and amino-imidazolines of fat acids, the aminoamides and amino-imidazolines of epoxidized fat acids, and the aminoamides and amino-imidazolines of polymeric fat acids.

3. In a process for the manufacture of felted fibrous cellulosic articles the step which comprises adding to the cellulosic fibrous material from about 0.1% to about 10% based on dry weight of cellulosic fiber, of a mixture comprising (A) from about 15 to about 85 percent by weight of an essentially completely oxidized (dialdehyde) starch, and (B) from about 85 to about 15 percent by weight of a fat acid derived amino-containing compound having an amine number from about 50 to about 700 selected from the group consisting of the aminoamides and amino-imidazolines of fat acids, the aminoamides and amino-imidazolines of epoxidized fat acids, and the aminoamides and amino-imidazolines of polymeric fat acids.

4. The composition comprising (A) from about 15 to about 85 percent by weight of a modified polysaccharide selected from the group consisting of oxidized polygalactomannan gums, and oxidized starches, and (B) from about 85 to about 15 percent by weight of a fat acid derived amino-containing compound having an amine number from about 50 to about 700 selected from the group consisting of the aminoamides and aminoimidazolines of fat acids, the aminoamides and aminoimidazolines of epoxidized fat acids, and the aminoamides and amino-imidazolines of polymeric fat acids.

5. The composition comprising (A) from about 15 to about 85 percent by weight of a polygalactomannan gum modified by treatment with from 0.01 to 0.4 moles periodate per mole of anhydrous hexose unit and (B) from about 85 to about 15 percent by weight of a fat acid derived amino-containing compound having an amine number from about 50 to about 700 selected from the group consisting of the aminoamides and amino-imidazolines of fat acids, the aminoamides and amino-imidazolines of epoxidized fat acids, and the aminoamides and amino-imidazolines of polymeric fat acids.

11 V a v. a 12 6. The composition comprising (A) from about 15 8. A felted fibrous cellulosic product (treated in acto about 85 percent by Weight of an essentially comcordance with claim 7) having added to the fibers pletely oxidized (dialdehyde) starch, and (B) from about thereof the composition of claim 4. 85 to about 15 percent by Weight of a fat acid derived amino-containing compound having an amine number 5 References Cited in the file of this Patent from about 50 to about 700 selected from the group UNITED STATES PATENTS consisting of the aminoamides and amino-imidazolines 2,772,969 Reynolds a1. Dec. 4, 1956 of fat acids, the aminoamides and amino-imidazolines of epoxidized fat acids, and the aminoamides and amino- OTHER REFERENCES imldazolinfis of fat i 10 Jones et al.: Tappi, vol. 42 (10), pages 862-66 7. The process which comprises lrnprcgnatlon of felted (1959) fibrous cellulosic material with the composition of Sloan et 1 Industrial and Engineering chemistry,

claim 4. pages 1165-72, July 1956.

, UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No: 3 138 473 June 23,, 1964 Don Floyd et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3,, line 37 for "invoving" read involving column l lines 60 to 67 second formula for the lower portion thereof reading \a H/ l-l/ W E E column 7 first table in the heading to the second 0011111111., and in the sub-headings to columns 3 and 4 thereof for "GJ each occurrence read g --g column 8 line 30 for "tail" read tall e Signed and sealed this 19th day of January 1965.

(SEAL) Attest:

ERNEST W, SWIDER EDWARD J, BRENNER Attesting Officer Commissioner of Patents 

4. THE COMPOSITION COMPRISING (A) FROM ABOUT 15 TO ABOUT 85 WEIGHT OF A MODIFIED POLYSACCHARIDE SELECTED FROM THE GROUP CONSISTING OF OXIDIZED POLYGALACTOMANNAN GUMS, AND OXIDIZED STARCHES, AND (B) FROM ABOUT 85 TO ABOUT 15 PERCENT BY WEIGHT OF A FAT ACID DERIVED AMINO-CONTAING COMPOUND HAVING AN AMINE NUMBER FROM ABOUT 50 TO ABOUT 700 SELECTED FROM THE GROUP CONSISTING OF THE AMINOAMIDES AND AMINOIMIDAZOLINES OF FAT ACIDS, THE AMINOAMIDES AND AMINOIMIDAZOLINES OF EPOXIDEZED FAT ACIDS AND THE AMINOAMIDES AND AMINO-IMIDAZOLINES OF POLYMERIC FAT ACIDS. 